Process of treating petroleum-oils.



Patented Aug. 6,` 1918.-

3 SHEETS-SHEET l.

W. F. NI. NICCARTY.-

APPLICATION FILED AuG.17.1svs.

PROCESS 0F TREATING PETROLEUM OILS.A

l w. F. M. MCCARTY.l PROCESSl OF TREATING'PEROLEUNL OILS.

'APPLICATION FILED AUG. I7. 1916.

Patented Aug. 6, 1918.

A 3 SHEETS-SHEET 2.

gfvvfnfoz //f'/f W. F. IVI. NICCARTY. PROCESS 0F TREATI'NG PETROLEUM OILS. APPLICATION FILED Aua.11.19,16.

A. Patented ug. 6, 1918.

3 SIIIEISTS-SHIEET 3.4

`provements in Processes of Treating UNITED STATES PATENTv oFF-Ion.

WILLIAM r. MAsoN MocAn'rY, oEBALTIMonE, MARYLAND.

PROCESS 0F TREATING-PETROLEUM-OILS.

To all wliom z't may concern: .i

Be it known that I, Wmmmin M.Me

QARTY, a citizen of the United States, residingat Baltimore, in the State of Maryland,

have invented certain new and useful Im- Petroleum-Oils, of which the following is a treating crude petroleum or'a petroleum oil or, fraction having a higher boiling point than gasolene, to produce an increased yield of asolene and more or less similar volatile hy rocarbons adapted for use as motor fuels, and, in its preferred embodiment, -my improved process is designed to 'effect the production from petroleumiiaterial and particularly crude petroleum, of. not only gasolene like bodies adapted foruse as motor fuels but aromatic hydrocarbons 'and par-v ticularlybenz-in and toluene adapted for use t in the manufacture of explosives.

Iny the practice of my process, in its preferred embodiment, petroleum oil, preferably crude oil, isheated in the presence of an aluminum' salt such as the chlorid or sulfate of aluminum and water.4 :I prefer to add to the petroleum in a suitable receptacle, five per cent. of its weight of water containin five per cent.' by weight ofl aluminum su fate or alum. The receptacle is then hermetically sealed and superheated steam preferably under a pressure of about 150 pounds per square inch is introduced for a period of preferably from fifteen minutes to thirty minutes. 'As a result of this action a mix-V ture is produced; The steam is then shut off I .and the water contained in the oil is allowed to settle and is then drawn off.y It is obvious that the alum serves as al reinin agent, to... drag down tarry matter Vand .ot er impurities in the oil, the same being removed from the oilwhen the water is withdrawn as above stated. After the withdrawal of the water, steam is again introduced into the treated petroleum material, preferably un-v der a pressure 'of 1 50 pounds per square inch until the temperature of the oil is raised to preferably from 250 to 300 C. The treated oil is then caused to pass through a superheating coil maintained at a temperature of preferably 400 C. It is then .intimately mixed with hydrogen preferably in the pro- A portions of one part by weight of'hydrogen to 500 parts by weight of the va orlzed oil. The proportionof hydrogen use' should be Specification of Letters Patent.

through a crackingtube or retort which isA preferably maintalned at a` constant temperature of 600 C., and in this cracking tube or retort the mixture .is subjected to the action of catalytic metal, preferably nickel. The pressure in the cracking tube orretort is preferably maintained at about fifty pounds per square inch. Under these .conditions thepetroleum'A material under treatment is decomposed with thelproduction of the maximum production of gasolene like materials, benzin and toluene and a minimum production tarry matters.

The products of decomposition are passed from the cracking tube or retort into ra .suit- Fable condenser where the condensable hydrocarbons arer separated and the gaseous portion of the decomposition-products is collected in a suitable gas holder.y l I have found that improved results over those resulting from the processes now com'- Patented Aug'. 6, 1918. Application m'ed'Augqst 17,1916. serial myuasls. i l

of gas, carbon and monly in use may be obtained without the preliminary treatment of the petroleum material with an aluminum-salt but-improved results are obtained where the preliminary treatment withvthe aluminum salt isl carried out.

I have also .found that particularly good results are obtained by using hydrogen ina nascent state, that yis tosay, immediately upon its production.

In the accompanying drawings formlng a part of this specification and in which like numerals areemployed to designate like parts throughout the same,

Figure 1 isa side elevation of apparatus preferably employed in the practlce of my process', v.

Fig. 2 is a yhorizontal sectlonal view through a retort, taken on l1ne` 2 2 of Fig.

Fig. 3 is a' central vertical longitudinal sectionalview through the retort,

Fig. 4 isa similar view through the lower end vof the retort, .the upper portion thereof being broken awayf-`- Fig. 5 is a horizontal sectional View taken on line 5--5 of Fig. 4,'

Fi 6 is a similar view taken on line 6-6 of F1g.4, g

Fig. 7 is an enlarged fra entary tional view through'the cracklng or heatmg which is connectedan oil supply pipe 16.

This pipe 16 is equipped with a cut off valve v 17. A water supply pipe 18 is also connected with the upper end of the receptacle 15 and has a cut off valve 19. Leading into the upper end vof the receptacle 15 and extending therein to terminate near and spaced from its bottom, is a steam supply pipe 20, having a cut off valve 21. The receptacle 15 'is provided at its bottom with afwater draw-off or drain pipe 22, having a cut off valve 23. Connected with the receptacle 15, preferably near its lower end, is a take ofi'l pipe 24, leading into a super-heater 25, and having connection with the lower end of a coil 26 thereof. The upper end of the coil 26 is connected with a pipe 27, for a purpose to-be described.

The pipe 27 is provided with a plurality of branches 28, leading into retorts 29. As more clearly shown in Fig. 3, each branch 28 is equipped with a cut-off valve 30. Each retort 29 comprises an outer casing or body portion 31, -preferably lined with4 suitable.

heat' resisting material. The numeral 32 designates a heat generating device', such as oil or gas burners, adapted to provide flames which project inwardly within the casing 31, as is obvious. Thevfuelis supplied to the burners 32 through a pipe 33 or the like. v

Extending longitudinally and centrally within the casing 31 is -an inclosing conduit 33, which is preferably square in lcross-section and formed of heat resistingmaterial.u

This conduit is held in place by spacing elements 34, as shown. The upper end ofthe inclosing conduitV 33 is open and in free communication with the interior of the-retort casing 31, while its lower end is closed and connected with an outlet 35, in turn connected with a stack 36. Extending longi" tudinally Within theconduit 33 is a cracking tube 37, the upper end of which is provided with a cap 38.

The numeral 39 designates a sleeve, `provided at its'upper end with a Hange40, arranged ,beneath the cap 3 8 and upon -the upper flanged end of thetube 37. These d flanges are secured together by bolts 41 or the like. AThe lower end of thetube 39'is provlded with a casting or nozzle 42, having an outlet opening 43, which flares downwardly, for spraying the oiljLeading intol the outlet opening 43 is a vapor or hydrogen supply pipe 44, having a cut off valve 45. The vaporized oil and hydrogen', which become intimately mixed in the opening of the nozzle v42, spray downwardly and impinge .against a curved stationary baffle plate' 46,

which `deflectsthe gaseous mixture laterally Extending longitudinally within the cracking tube 37 is a reciprocatory and rotatable into'the upper 'end of the cracking tube 37.

rod 47, to which are secured agitator or scraping elements or paddles 48, which are formed partly or Wholly ,of catalytic material, such as nickel, while other catalytic material may be employed. The rod 47 is. journaled through a suitable bearing 49,

and the lower end of this rod carries annular flanges or disks 50, rigidly secured thereto.

' Arranged between the flanges 50 is a cam 51,

carried by a shaft'52. The shaft 52 is driven by a bevel gear.53, (see Fig. 4) engaging av worm' wheel is driven by'a worm 58, carried by the shaft 59. The shaft 59 i's rotated by any suitable means and at a desired speed.

V.Connected with the lower end of the -A cracking tube 37, as more clearly shown in Figs. 4 and 5, is an enlarged collecting chamber 60,in the bottom of which is mounted to rotate a scraper 61. Thisscraper is carried by the sleeve 56 and rotates therewith. The agitators or Scrapers 48, by their combined rotatable and reciprocatory movements, serve to remove the carbon deposits from the interior of the cracking tube 37,

and these deposits, together' -Withmore or less uncracked oil, gravitate into the chamber 60and are subjected to ,the action of the rotating agitator 61. The. carbon deposits, with more or lessV oil, discharge from' the chamber 60, through a conduit 62, into a holdingtank 63. The carbon withpthe oil,

lwhich passes into the tank 63, are allowed to settle and the oil may-be withdrawn through Y 4 i,

a `pipe 64, having a cut off valve 65', while the carbon gravitatesvinto a trap 65, having 1 a door 66, and may-be removed therefrom.

As more clearly shown in Fig. 3, each.

-Leading into each chamber 60, is yan oil draw-0H pipe 68, the intake end of which' is arranged 'near and above the agitator 61. The pipe 68 has a cut ofl" valve 69. The un-l tend to separate toa certain extent, and the o1l on top 1s withdrawn through the pipe cracked oil and carbon, in the chamber 60,

l which do not condense discharge from the 6.8. The oil in the pipe 68 may be pumped l back into the shell 15 and again treated by theoperation of the several'retorts are idenpassing through the apparatus'. Y .The take olf pipes 67 for the gaseousl products of distillation, discharge into a common pipe70, which conduct the gases to traps 71,.

for depriving the same ofvwater. The gases are then passed by the pipe 70 into a coil 72 of a condenser. The lower end of theJ coil 72 ldischarges into a trap 74, wherein the condensed gases are collected and may be withdrawn through a pipe 75. The gases trap74 into a pipe 75, which leads into a gas holding tank 7 6; 'l

In the practice of my process in connection with the apparatus herewith shown and described, the oil, such as crude petroleum oil, is introduced into the closed receptacle 15 through 4the pipe 16, and the valve 17 is closed. The valve 19' is opened and water, in the proportions of five per cent. by weight'4 of water ivith-respect to the weight of oil, vsuch water containing five per cent. by weight of an aluminum salt, such as alum, aluminum, clilorid, oraluininum'sulfate, is fed through the pipe 18 into the closed receptaele 15, in the presence of the `oil.k The valve 19 is closed and the valve 23V is also closed. 'The steam valve 21'.is now opened, and' super-heated steam, preferably under a pressure'of about 150 pounds to the square inch is introduced into the receptacle- 15 forV a'period of preferably from 15 minutes to v minutes. As a result of this action, the

oil and water are'thoroughly agitated in the presence of heat and pressure and a mixture is produced. The formation ofdesired decomposition productsl during the cracking operation is materially aided by the prior treatment with steam and kalum or 'other aluminum lcompounds as hereinbefore described. The steam valve 21"is now closed andl the contents of the receptacle 15is allowed to settle so that the water may 1be t e valve 23. It is obvious that the alum in the Water serves as a. refining agent to drag down the tarry matter and other impurities, l

which are removed from the oil, when the water is withdrawn, as above stated.' .This valve 23 is again closed` and the steam valve 21'is again opened, so that steam' is supplied -into the receptacle `15 in the presence of the oil. such steam being preferably under a pressure of 150 pounds persqiiare inch. until the temperature of the oil. is raised to pref` erably 250 to 300 C. The valve 24" in the pipe 24C maintained at a temperature of 4100o C. Iii

-the super-heatingl coiLthe oil is vaporized hereinabove explained.

is now opened, and the pressure inthe receptacle 15 forces the oil into the .super-heating coil 26, .which is preferably torts, for treatment therein, and such treatment in only one retort will' be given, since tical. l'By tui-ning to Fig-3 of the drawings, it willbe seen that the gasiied oil dis# charges-through the pipe 28 into the tube 39, and then passes ,into the spraying nozzle f' 42. In this spraying-nozzle the gasified oil is intimately mixed with incoming hydrogen` gas supplied through the pipe 44, and this mixture of the gaseous oil and hydrogen gas 4 .impinges upon the baille plate 46. The hydrogen gas isv preferably supplied vto the gaseous oil in the proportions of one part I by weight of hyrogen to five hundred parts by weight of the gaseous" oil. The proportions of hydrogen should be siiliicient to saturate the unsaturated molecules in the gaseous emulsion and an excess of hydrogen should be used. The mixture of the gaseous oil and hydrogen discharge into the crack- 48. The pressure inl the cracking` tube .is preferably maintained at about 50 pounds to the square inch. While the gaseous mixture is undergoing; treatment in .the cracking tiibe,'as above indicated, the rod -17 is conspeeds. The agitators 48 keep the gaseous mixture ina suitable state of agitation, whereby they are maintained atthe uniform temperature of the tube 37, to wit, 600 C. The agitators 48, by reciprocating and rotating in close proximity'to the inner wall of the tube' 37, serve to remove therefrom the carbon deposits which gravit-ate into the chamber 61,'with nioreor less uncracked oil, and the same are removed therefrom, as Under the above stated conditionsl of treatment, the oil or they petroleum material, is decomposed with the 'stantly recprocated and rotated at suitable y production of. the maximum yield of gaso- I lene like materials, benzinand vtoluene and the minimum yield of gas, carbon, and tarry matters. Y

These gaseous products fot' distillation are conducted through pipe 70 andiniss-throiigh the traps 71,' to remove the water therefrom.

The gaseous products then pass into the coil 72 of the condenser. wherein a part is eondensed';l the hydrocarbons then pass to the` trap 47-1: and are separated from the gaseous hydrocarbons. The condensed hydrocarbons are collected within the trap 74 and iiiav be. removed therefrom to the pipe 75. wlii-lethe gaseous h i-droearbons pass through thel pipe 75 into the gas holding tank76.v

The"apparatus shown and described in` this` application is not claimed herein as the same, disclosed and claimed in luy-cos pending application for apparatus for treating petroleum oils, Serial N o. 115,514.

It is to be understood that the form of my invention herewith shown and described is filed August 17th, 1916',

'to be taken as a preferred example of the same, and that various changes may be resorted to in the order vof the steps of the process,'the temperatures employed in the treatment of the material, and the general procedure of the process, without departing from the spirit of my invention or the scope of the subjoined claims.

Having thus describedmy invention, Iv

Y the mass to settle, withdrawing the water and the material held in solution or suspension therein from the oil, subjecting the oil thus treated to the action of heat at substantially 4000 C. for vaporizing the same,

subjecting the Vaporized oil to a temperature of substantially 600 C. in the presence of hydrogen and a catalytic agent for de-I composing the same, and condensing the condensable portion of the decomposition products.

2. The lhereindescribed process of' treat--A ing petroleum oils,.fractions and. the like having a higher boiling point than gasolene, which consists in subjecting the oil to the actioh 300 C., in the prsence of water'and a waof heat from substantially 250 to ter soluble aluminum compound, allowing the mass tov settle, withdrawing the water and the material held in solution or suspension therein from the oil, subjecting the oil thus treated to the action of heat to Vaporize the same, subjecting the vaporized oil to a temperature of approximately 600o C., andv a pressure of approximately pounds to the square inch, in the presence of hydrogen and a catalytic agent to decompose the va- ,porized oil, and condensing the condensable` portion of the decomposition products.

In testimony whereof I aflixmy signature v in presence of two Witnesses.

WILLIAM F. MASON MCCARTY. Witnesses:

C. L. PARKER, j

ARTHUR L. BRYANT. 

